Multi-mass velocity map imaging study of the 805 nm strong field ionization of CF 3 I.

Multi-mass velocity map imaging studies of charged fragments formed by near infrared strong field ionization together with covariance map image analysis offer a new window through which to explore the dissociation dynamics of several different highly charged parent cations, simultaneously - as demonstrated here for the case of CF 3 I Z + cations with charges Z ranging from 1 to at least 5. Previous reports that dissociative ionization of CF 3 I + cations yields CF 3 + , I + and CF 2 I + fragment ions are confirmed, and some of the CF 3 + fragments are deduced to undergo secondary loss of one or more neutral F atoms. Covariance map imaging confirms the dominance of CF 3 + + I + products in the photodissociation of CF 3 I 2+ cations and, again, that some of the primary CF 3 + photofragments can shed one or more F atoms. Rival charge symmetric dissociation pathways to CF 2 I + + F + and to IF + + CF 2 + products and charge asymmetric dissociations to CF 3 + I 2+ and CF 2 I 2+ + F products are all also identified. The findings for parent cations with Z ≥ 3 are wholly new. In all cases, the fragment recoil velocity distributions imply dissociation dynamics in which coulombic repulsive forces play a dominant role. The major photoproducts following dissociation of CF 3 I 3+ ions are CF 3 + and I 2+ , with lesser contributions from the rival CF 2 I 2+ + F + and CF 3 2+ + I + channels. The CF 3 2+ fragment ion images measured at higher incident intensities show a faster velocity sub-group consistent with their formation in tandem with I 2+ fragments, from photodissociation of CF 3 I 4+ parent ions. The measured velocity distributions of the I 3+ fragment ions contain features attributable to CF 3 I 5+ photodissociation to CF 3 2+ + I 3+ and the images of fragments with mass to charge ( m / z ) ratio ∼31 show formation of I 4+ products that must originate from parent ions with yet higher Z .